Tackifier compounds and methods of using the same

ABSTRACT

The present invention relates to tackifier compounds and methods of using the same. In various embodiments, the present invention provides a tackifier compound including independently substituted or unsubstituted fused rings A and B each independently chosen from (C 5 -C 10 )cycloalkyl and (C 2 -C 10 )heterocyclyl. Fused ring A is substituted with (R 1 ) 1-8  and fused ring B is substituted with —(OC(O)R′C(O)R 2 ) 1-8 . At each occurrence R′ is independently chosen from (C 2 -C 10 )alkanylene, (C 2 -C 10 )alkenylene, (C 2 -C 10 )alkynylene, C 5 -C 20 (arylene), and (C 1 -C 20 )heteroarylene, wherein R′ is unsubstituted or substituted. At each occurrence R 1  is independently selected from —OH, —OR 3 , and —OC(O)R′C(O)R 2 . At each occurrence R 2  is independently chosen from —OH, —OR 3 , —NH 2 , —NHR 3 , and —NR 3   2 . At each occurrence R 3  is independently chosen from (C 1 -C 10 )alkanyl, (C 2 -C 10 )alkenyl, (C 2 -C 10 )alkynyl, C 5 -C 20 (aryl), and (C 1 -C 20 )heteroaryl, wherein R 3  is unsubstituted or substituted.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/434,719, filed Apr. 9, 2015, now issued as U.S. Pat. No. 9,688,794,which is a U.S. National Stage Filing under 35 U.S.C. 371 fromInternational Application No. PCT/US2013/064960, filed on 15 Oct. 2013and published as WO 2014/062625 on 24 Apr. 2014, which claims thebenefit of priority to U.S. Provisional Patent Application Ser. No.61/872,116 entitled “TACKIFIER COMPOUNDS AND METHODS OF USING THE SAME,”filed Aug. 30, 2013, and also claims the benefit of priority to U.S.Provisional Patent Application Ser. No. 61/713,889 entitled“POLYISOCYANATES FROM FUSED BICYCLIC POLYOLS AND POLYURETHANESTHEREFROM,” filed Oct. 15, 2012, which applications and publications areincorporated herein in their entirety by reference.

BACKGROUND OF THE INVENTION

Tackifiers are materials that have a characteristic of immediatetackiness or stickiness. Tackifiers can be used in a wide variety ofapplications, and often form a major component of adhesive compositions.Examples of tackifiers include rosins, terpenes and modified terpenes,petroleum-derived resins, terpene-phenol resins, and silicone resins.Tackifiers can be expensive, and are frequently the most costlycomponent of adhesive formulations. Tackifiers are frequently derivedfrom non-biorenewable materials.

SUMMARY OF THE INVENTION

In various embodiments, the present invention provides a tackifiercompound having the structural formula

or a salt thereof. Fused rings A and B are each independently chosenfrom (C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and nare each independently 1-8. At each occurrence R¹ is independentlyselected from —OH, —OR³, and

At each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J. At each occurrence R² is independently chosen from —OH,—OR³, —NH₂, —NHR³, and —NR³ ₂. At each occurrence R³ is independentlychosen from (C₁-C₁₀)alkanyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl, wherein R³ is unsubstituted orsubstituted with at least one J. Fused rings A and B are eachindependently unsubstituted or substituted with at least one of J,(C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl,(C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy, (C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl,(C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl, (C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or(C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; wherein each alkyl, alkenyl, alkynyl,haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, andheteroaryl is independently unsubstituted or further substituted with atleast one J. The variable J independently at each occurrence is chosenfrom F, Cl, Br, I, OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O),methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R,C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, OC(O)OR,C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R,N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR,N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(C(O)R)C(O)R,N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, and C(═NOR)R, wherein R isindependently at each occurrence chosen from hydrogen, (C₁-C₁₀)alkyl,(C₁-C₁₀)cycloalkyl, (C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl,(C₁-C₁₀)aralkyl, (C₁-C₁₀)heterocyclyl,(C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl, (C₁-C₁₀)heteroaryl, and(C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein each alkyl, cycloalkyl,cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl,heteroaryl, and heteroarylalkyl is independently unsubstituted orsubstituted with 1-3 J.

In various embodiments, the present invention provides a polymercomprising a repeating unit having the structure

or a salt thereof. Fused rings A and B are each independently chosenfrom (C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and nare each independently 1-8. At each occurrence R⁴ is independentlyselected from —OH, —OR³,

At each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₂-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J. At each occurrence R″ is independently a(C₂-C₁₀)alkanylene bonded to at least one of a repeating unit and anend-blocking unit of the polymer at two locations, wherein R″ isunsubstituted or substituted with at least one J. At each occurrence R²is independently chosen from —OH, —OR³, —NH₂, —NHR³, and —NR³ ₂. At eachoccurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J. Fusedrings A and B are each independently unsubstituted or substituted withat least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)haloalkoxy, (C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl,(C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl, (C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or(C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; wherein each alkyl, alkenyl, alkynyl,haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, andheteroaryl is independently unsubstituted or further substituted with atleast one J. The variable J independently at each occurrence is chosenfrom F, Cl, Br, I, OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O),methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R,C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, OC(O)OR,C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R,N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR,N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(C(O)R)C(O)R,N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, and C(═NOR)R, wherein R isindependently at each occurrence chosen from hydrogen, (C₁-C₁₀)alkyl,(C₁-C₁₀)cycloalkyl, (C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl,(C₁-C₁₀)aralkyl, (C₁-C₁₀)heterocyclyl,(C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl, (C₁-C₁₀)heteroaryl, and(C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein each alkyl, cycloalkyl,cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl,heteroaryl, and heteroarylalkyl is independently unsubstituted orsubstituted with 1-3 J.

In various embodiments, the present invention provides a systemincluding the tackifier compound having the structure

or the salt thereof. The system also includes a first substrate. Thetackifier compound is bonded to the first substrate.

In various embodiments, the present invention provides a systemincluding the polymer including a repeating unit having the structure

or the salt thereof. The system also includes a first substrate. Thepolymer is bonded to the first substrate.

In various embodiments, the present invention provides a method of usingthe tackifier compound having the structure

or the salt thereof. The method includes contacting the tackifiercompound to a first substrate such that the tackifier is bonded to thefirst substrate.

In various embodiments, the present invention provides a method ofmaking the tackifier compound. The method includes contacting a compoundhaving the structure

and an acid anhydride having the structure

to provide the tackifier compound having the structure

or the salt thereof.

In various embodiments, the present invention provides certainadvantages over other tackifier compounds or methods of making and usingtackifier compounds, at least some of which are unexpected. For example,in some embodiments, the tackifier compound can have greater tackinessthan other tackifiers. In some embodiments, the tackifier compound canbe made for a lower cost than other tackifiers, or at a cost competitivewith that of other tackifiers. In some embodiments, the tackifier canprovide a greater amount of tackiness for a particular cost than thatprovided by other tackifiers. In some embodiments, the method of makingthe tackifier compound can require little to no purification, providinga method that requires less purification than other methods. In someembodiments, the properties of the tackifier, such as solubility inwater, glass transition temperature, and tackiness, can be more easilyadjusted or tuned by varying the starting materials than is possiblewith other tackifiers. In some embodiments, the tackifier is also usefulas a rheology modifier, such as a thickener or viscosifier, such as inorganic liquids, oils, or aqueous liquids.

In some embodiments, the tackifier compound can be generated frombiorenewable sources. In some embodiments, the tackifier compound can begenerated from more readily available or cheaper biorenewable sourcesthan other tackifiers. In some embodiments, the tackifier compound canbe generated from biorenewable sources more easily and with less costthan other tackifiers. In some embodiments, the tackifier compound canbe made from a greater proportion of biorenewable materials than othertackifiers. In some embodiments, the method of making the tackifier canbe more environmentally friendly than other methods; for example, insome embodiments, the method can use less solvent or can generate lesswaste than other procedures. In some embodiments, the tackifier compoundcan cost less than or can have a cost competitive with the cost ofpetroleum-derived tackifiers. In some embodiments, the process of makingthe tackifier can be more easily scalable than other methods, such asother methods of making tackifiers from biorenewable sources. In someembodiments, the method of making the tackifier compound can transform acompound, such as isosorbide, isomannide, or isoidide, into a usefulsubstance for a lower cost, greater convenience, or with lessenvironmental impact, than other methods of transforming of modifyingthe compound.

In some embodiments, unlike other tackifiers, the tackifier can be acurable tackifier that hardens into a strongly-bonding material. In someembodiments, the property of curability can provide a greater number ofor different types of uses than those practically available with othertackifiers. In some embodiments, curability can allow for modificationof properties via a variety of external stimuli. In some embodiments,the curable tackifier can be cured using different methods or using agreater variety of methods than possible with other tackifiers. In someembodiments, unlike other tackifiers, the curable property of thetackifier can allow the tackifier to serve as a greater proportion of anadhesive composition or as substantially the only component of anadhesive composition.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g.,0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.The statement “about X to Y” has the same meaning as “about X to aboutY,” unless indicated otherwise. Likewise, the statement “about X, Y, orabout Z” has the same meaning as “about X, about Y, or about Z,” unlessindicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.In addition, it is to be understood that the phraseology or terminologyemployed herein, and not otherwise defined, is for the purpose ofdescription only and not of limitation. Any use of section headings isintended to aid reading of the document and is not to be interpreted aslimiting; information that is relevant to a section heading may occurwithin or outside of that particular section. Furthermore, allpublications, patents, and patent documents referred to in this documentare incorporated by reference herein in their entirety, as thoughindividually incorporated by reference. In the event of inconsistentusages between this document and those documents so incorporated byreference, the usage in the incorporated reference should be consideredsupplementary to that of this document; for irreconcilableinconsistencies, the usage in this document controls.

In the methods of manufacturing described herein, the steps can becarried out in any order without departing from the principles of theinvention, except when a temporal or operational sequence is explicitlyrecited. Furthermore, specified steps can be carried out concurrentlyunless explicit claim language recites that they be carried outseparately. For example, a claimed step of doing X and a claimed step ofdoing Y can be conducted simultaneously within a single operation, andthe resulting process will fall within the literal scope of the claimedprocess.

Selected substituents within the compounds described herein are presentto a recursive degree. In this context, “recursive substituent” meansthat a substituent may recite another instance of itself or of anothersubstituent that itself recites the first substituent. Recursivesubstituents are an intended aspect of the disclosed subject matter.Because of the recursive nature of such substituents, theoretically, alarge number may be present in any given claim. One of ordinary skill inthe art of organic chemistry understands that the total number of suchsubstituents is reasonably limited by the desired properties of thecompound intended. Such properties include, by way of example and notlimitation, physical properties such as molecular weight, solubility,and practical properties such as ease of synthesis. Recursivesubstituents can call back on themselves any suitable number of times,such as about 1 time, about 2 times, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20,30, 50, 100, 200, 300, 400, 500, 750, 1000, 1500, 2000, 3000, 4000,5000, 10,000, 15,000, 20,000, 30,000, 50,000, 100,000, 200,000, 500,000,750,000, or about 1,000,000 times or more.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “organic group” as used herein refers to but is not limited toany carbon-containing functional group. For example, anoxygen-containing group such as alkoxy groups, aryloxy groups,aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups includingcarboxylic acids, carboxylates, and carboxylate esters; asulfur-containing group such as alkyl and aryl sulfide groups; and otherheteroatom-containing groups. Non-limiting examples of organic groupsinclude OR, OOR, OC(O)N(R)₂, CN, CF₃, OCF₃, R, C(O), methylenedioxy,ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R,C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂, N(R)N(R)C(O)R, N(R)N(R)C(O)OR,N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R,N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(═NH)N(R)₂,C(O)N(OR)R, or C(═NOR)R wherein R can be hydrogen (in examples thatinclude other carbon atoms) or a carbon-based moiety, and wherein thecarbon-based moiety can itself be further substituted.

The term “substituted” as used herein refers to an organic group asdefined herein or molecule in which one or more hydrogen atoms containedtherein are replaced by one or more non-hydrogen atoms. The term“functional group” or “substituent” as used herein refers to a groupthat can be or is substituted onto a molecule, or onto an organic group.Examples of substituents or functional groups include, but are notlimited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groupssuch as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxygroups, oxo(carbonyl) groups, carboxyl groups including carboxylicacids, carboxylates, and carboxylate esters; a sulfur atom in groupssuch as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups,sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atomin groups such as amines, hydroxylamines, nitriles, nitro groups,N-oxides, hydrazides, azides, and enamines; and other heteroatoms invarious other groups. Non-limiting examples of substituents J that canbe bonded to a substituted carbon (or other) atom include F, Cl, Br, I,OR, OC(O)N(R′)₂, CN, NO, NO₂, ONO₂, azido, CF₃, OCF₃, R′, O (oxo), S(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR,SO₂R′, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR,OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R,(CH₂)₀₋₂N(R)N(R)₂, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)Rwherein R can be hydrogen or a carbon-based moiety, and wherein thecarbon-based moiety can itself be further substituted; for example,wherein R can be hydrogen, alkyl, acyl, cycloalkyl, aryl, aralkyl,heterocyclyl, heteroaryl, or heteroarylalkyl, wherein any alkyl, acyl,cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkylor R can be independently mono- or multi-substituted with J; or whereintwo R groups bonded to a nitrogen atom or to adjacent nitrogen atoms cantogether with the nitrogen atom or atoms form a heterocyclyl, which canbe mono- or independently multi-substituted with J.

The term “alkyl” as used herein refers to straight chain and branchedalkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from1 to 8 carbon atoms. Examples of straight chain alkyl groups includethose with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples ofbranched alkyl groups include, but are not limited to, isopropyl,iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompassesn-alkyl, isoalkyl, and anteisoalkyl groups as well as other branchedchain forms of alkyl. Representative substituted alkyl groups can besubstituted one or more times with any of the groups listed herein, forexample, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, andhalogen groups.

The term “alkenyl” as used herein refers to straight and branched chainand cyclic alkyl groups as defined herein, except that at least onedouble bond exists between two carbon atoms. Thus, alkenyl groups havefrom 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12carbons or, in some embodiments, from 2 to 8 carbon atoms. Examplesinclude, but are not limited to vinyl, —CH═CH(CH₃), —CH═C(CH₃)₂,—C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂, cyclohexenyl,cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienylamong others.

The term “alkynyl” as used herein refers to straight and branched chainalkyl groups, except that at least one triple bond exists between twocarbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 toabout 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments,from 2 to 8 carbon atoms. Examples include, but are not limited to—C≡CH, —C≡C(CH₃), —C≡C(CH₂CH₃), —CH₂C≡CH, —CH₂C≡C(CH₃), and—CH₂C≡C(CH₂CH₃) among others.

The term “acyl” as used herein refers to a group containing a carbonylmoiety wherein the group is bonded via the carbonyl carbon atom. Thecarbonyl carbon atom is also bonded to another carbon atom, which can bepart of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl,heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group orthe like. In the special case wherein the carbonyl carbon atom is bondedto a hydrogen, the group is a “formyl” group, an acyl group as the termis defined herein. An acyl group can include 0 to about 12-20 or 12-40additional carbon atoms bonded to the carbonyl group. An acyl group caninclude double or triple bonds within the meaning herein. An acryloylgroup is an example of an acyl group. An acyl group can also includeheteroatoms within the meaning here. A nicotinoyl group(pyridyl-3-carbonyl) is an example of an acyl group within the meaningherein. Other examples include acetyl, benzoyl, phenylacetyl,pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When thegroup containing the carbon atom that is bonded to the carbonyl carbonatom contains a halogen, the group is termed a “haloacyl” group. Anexample is a trifluoroacetyl group.

The term “cycloalkyl” as used herein refers to cyclic alkyl groups suchas, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, thecycloalkyl group can have 3 to about 8-12 ring members, whereas in otherembodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or7. Cycloalkyl groups further include polycyclic cycloalkyl groups suchas, but not limited to, norbornyl, adamantyl, bornyl, camphenyl,isocamphenyl, and carenyl groups, and fused rings such as, but notlimited to, decalinyl, and the like. Cycloalkyl groups also includerings that are substituted with straight or branched chain alkyl groupsas defined herein. Representative substituted cycloalkyl groups can bemono-substituted or substituted more than once, such as, but not limitedto, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups ormono-, di- or tri-substituted norbornyl or cycloheptyl groups, which canbe substituted with, for example, amino, hydroxy, cyano, carboxy, nitro,thio, alkoxy, and halogen groups. The term “cycloalkenyl” alone or incombination denotes a cyclic alkenyl group.

The term “aryl” as used herein refers to cyclic aromatic hydrocarbonsthat do not contain heteroatoms in the ring. Thus aryl groups include,but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl,indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl,naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.In some embodiments, aryl groups contain about 6 to about 14 carbons inthe ring portions of the groups. Aryl groups can be unsubstituted orsubstituted, as defined herein. Representative substituted aryl groupscan be mono-substituted or substituted more than once, such as, but notlimited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substitutednaphthyl groups, which can be substituted with carbon or non-carbongroups such as those listed herein.

The term “aralkyl” as used herein refers to alkyl groups as definedherein in which a hydrogen or carbon bond of an alkyl group is replacedwith a bond to an aryl group as defined herein. Representative aralkylgroups include benzyl and phenylethyl groups and fused(cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. Aralkenyl groupare alkenyl groups as defined herein in which a hydrogen or carbon bondof an alkyl group is replaced with a bond to an aryl group as definedherein.

The term “heterocyclyl” as used herein refers to aromatic andnon-aromatic ring compounds containing 3 or more ring members, of which,one or more is a heteroatom such as, but not limited to, N, O, and S.Thus a heterocyclyl can be a cycloheteroalkyl, or a heteroaryl, or ifpolycyclic, any combination thereof. In some embodiments, heterocyclylgroups include 3 to about 20 ring members, whereas other such groupshave 3 to about 15 ring members. A heterocyclyl group designated as aC₂-heterocyclyl can be a 5-ring with two carbon atoms and threeheteroatoms, a 6-ring with two carbon atoms and four heteroatoms and soforth. Likewise a C₄-heterocyclyl can be a 5-ring with one heteroatom, a6-ring with two heteroatoms, and so forth. The number of carbon atomsplus the number of heteroatoms sums up to equal the total number of ringatoms. A heterocyclyl ring can also include one or more double bonds. Aheteroaryl ring is an embodiment of a heterocyclyl group. The phrase“heterocyclyl group” includes fused ring species including those thatinclude fused aromatic and non-aromatic groups. For example, adioxolanyl ring and a benzodioxolanyl ring system (methylenedioxyphenylring system) are both heterocyclyl groups within the meaning herein. Thephrase also includes polycyclic ring systems containing a heteroatomsuch as, but not limited to, quinuclidyl. Heterocyclyl groups can beunsubstituted, or can be substituted as discussed herein. Heterocyclylgroups include, but are not limited to, pyrrolidinyl, piperidinyl,piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl,benzofuranyl, dihydrobenzofuranyl, indolyl, dihydroindolyl, azaindolyl,indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl,benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl,thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl,isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinylgroups. Representative substituted heterocyclyl groups can bemono-substituted or substituted more than once, such as, but not limitedto, piperidinyl or quinolinyl groups, which are 2-, 3-, 4-, 5-, or6-substituted, or disubstituted with groups such as those listed herein.

The term “heteroaryl” as used herein refers to aromatic ring compoundscontaining 5 or more ring members, of which, one or more is a heteroatomsuch as, but not limited to, N, O, and S; for instance, heteroaryl ringscan have 5 to about 8-12 ring members. A heteroaryl group is a varietyof a heterocyclyl group that possesses an aromatic electronic structure.A heteroaryl group designated as a C₂-heteroaryl can be a 5-ring withtwo carbon atoms and three heteroatoms, a 6-ring with two carbon atomsand four heteroatoms and so forth. Likewise a C₄-heteroaryl can be a5-ring with one heteroatom, a 6-ring with two heteroatoms, and so forth.The number of carbon atoms plus the number of heteroatoms sums up toequal the total number of ring atoms. Heteroaryl groups include, but arenot limited to, groups such as pyrrolyl, pyrazolyl, tetrazolyl,oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl,benzofuranyl, indolyl, azaindolyl, indazolyl, benzimidazolyl,azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl,imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl,xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl,tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroarylgroups can be unsubstituted, or can be substituted with groups as isdiscussed herein. Representative substituted heteroaryl groups can besubstituted one or more times with groups such as those listed herein.

Additional examples of aryl and heteroaryl groups include but are notlimited to phenyl, biphenyl, indenyl, naphthyl (1-naphthyl, 2-naphthyl),N-hydroxytetrazolyl, N-hydroxytriazolyl, N-hydroxyimidazolyl,anthracenyl (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophenyl(2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), indolyl, oxadiazolyl,isoxazolyl, quinazolinyl, fluorenyl, xanthenyl, isoindanyl, benzhydryl,acridinyl, thiazolyl, pyrrolyl(2-pyrrolyl), pyrazolyl (3-pyrazolyl),imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl),triazolyl(1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl 1,2,3-triazol-4-yl,1,2,4-triazol-3-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl),thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl,3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3-pyridazinyl,4-pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl,4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl(1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl,6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), benzo[b]furanyl(2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl,5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl,2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl),3-(2,3-dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl),5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl),7-(2,3-dihydro-benzo[b]furanyl), benzo[b]thiophenyl(2-benzo[b]thiophenyl, 3-benzo[b]thiophenyl, 4-benzo[b]thiophenyl,5-benzo[b]thiophenyl, 6-benzo[b]thiophenyl, 7-benzo[b]thiophenyl),2,3-dihydro-benzo[b]thiophenyl, (2-(2,3-dihydro-benzo[b]thiophenyl),dihydro-benzo[b]thiophenyl), 4-(2,3-dihydro-benzo[b]thiophenyl),dihydro-benzo[b]thiophenyl), 6-(2,3-dihydro-benzo[b]thiophenyl),dihydro-benzo[b]thiophenyl), indolyl (1-indolyl, 2-indolyl, 4-indolyl,5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl, 3-indazolyl,4-indazolyl, 5-indazolyl, 6 indazolyl, 7-indazolyl),benzimidazolyl(1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl,5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 8-benzimidazolyl),benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl), benzothiazolyl(1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl,6-benzothiazolyl, 7-benzothiazolyl), carbazolyl (1-carbazolyl,2-carbazolyl, 3-carbazolyl, 4-carbazolyl), 5H-dibenz[b,f]azepine(5H-dibenz[b,f]azepin-1-yl, 5H-dibenz[b,f]azepine-2-yl,5H-dibenz[b,f]azepine-3-yl, 5H-dibenz[b,f]azepine-4-yl,5H-dibenz[b,f]azepine-5-yl), 10,11-dihydro-5H-dibenz[b,f]azepine(10,11-dihydro-5H-dibenz[b,f]azepine-1-yl,10,11-dihydro-5H-dibenz[b,f]azepine-2-yl,10,11-dihydro-5H-dibenz[b,f]azepine-3-yl,10,11-dihydro-5H-dibenz[b,f]azepine-4-yl,10,11-dihydro-5H-dibenz[b,f]azepine-5-yl), and the like.

The term “heterocyclylalkyl” as used herein refers to alkyl groups asdefined herein in which a hydrogen or carbon bond of an alkyl group asdefined herein is replaced with a bond to a heterocyclyl group asdefined herein. Representative heterocyclyl alkyl groups include, butare not limited to, furan-2-yl methyl, furan-3-yl methyl, pyridine-3-ylmethyl, tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl.

The term “heteroarylalkyl” as used herein refers to alkyl groups asdefined herein in which a hydrogen or carbon bond of an alkyl group isreplaced with a bond to a heteroaryl group as defined herein.

The term “alkoxy” as used herein refers to an oxygen atom connected toan alkyl group, including a cycloalkyl group, as are defined herein.Examples of linear alkoxy groups include but are not limited to methoxy,ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples ofbranched alkoxy include but are not limited to isopropoxy, sec-butoxy,tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclicalkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can includeone to about 12-20 or about 12-40 carbon atoms bonded to the oxygenatom, and can further include double or triple bonds, and can alsoinclude heteroatoms. For example, an allyloxy group is an alkoxy groupwithin the meaning herein. A methoxyethoxy group is also an alkoxy groupwithin the meaning herein, as is a methylenedioxy group in a contextwhere two adjacent atoms of a structures are substituted therewith.

The terms “halo” or “halogen” or “halide” group, as used herein, bythemselves or as part of another substituent mean, unless otherwisestated, a fluorine, chlorine, bromine, or iodine atom, preferably,fluorine, chlorine, or bromine.

The term “haloalkyl” group, as used herein, includes mono-halo alkylgroups, poly-halo alkyl groups wherein all halo atoms can be the same ordifferent, and per-halo alkyl groups, wherein all hydrogen atoms arereplaced by halogen atoms, such as fluoro. Examples of haloalkyl includetrifluoromethyl, 1,1-dichloroethyl, 1,2-dichloromethyl,1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

The term “hydrocarbon” as used herein refers to a functional group ormolecule that includes carbon and hydrogen atoms. The term can alsorefer to a functional group or molecule that normally includes bothcarbon and hydrogen atoms but wherein all the hydrogen atoms aresubstituted with other functional groups.

The term “resin” as used herein refers to polysiloxane material of anyviscosity that includes at least one siloxane monomer that is bonded viaa Si—O—Si bond to three or four other siloxane monomers. In one example,the polysiloxane material includes T or Q groups, as defined herein.

The term “number-average molecular weight” as used herein refers to theordinary arithmetic mean of the molecular weight of individual moleculesin a sample. It is defined as the total weight of all molecules in asample divided by the total number of molecules in the sample.Experimentally, the number-average molecular weight (M_(n)) isdetermined by analyzing a sample divided into molecular weight fractionsof species i having n_(i) molecules of molecular weight M_(i) throughthe formula M_(n)=ΣM_(i)n_(i)/Σn_(i). The number-average molecularweight can be measured by a variety of well-known methods including gelpermeation chromatography, spectroscopic end group analysis, andosmometry. If unspecified, molecular weights of polymers given hereinare number-average molecular weights.

The term “weight-average molecular weight” as used herein refers(M_(w)), which is equal to ΣM_(i) ²n_(i)/ΣM_(i)n_(i), where n_(i) is thenumber of molecules of molecular weight M_(i). In various examples, theweight-average molecular weight can be determined using lightscattering, small angle neutron scattering, X-ray scattering, andsedimentation velocity.

The term “radiation” as used herein refers to energetic particlestravelling through a medium or space. Examples of radiation are visiblelight, infrared light, microwaves, radio waves, very low frequencywaves, extremely low frequency waves, thermal radiation (heat), andblack-body radiation.

The term “cure” as used herein refers to exposing to radiation in anyform, heating, or allowing to undergo a physical or chemical reactionthat results in hardening or an increase in viscosity.

The term “solvent” as used herein refers to a liquid that can dissolve asolid, liquid, or gas. Nonlimiting examples of solvents are silicones,organic compounds, water, alcohols, ionic liquids, and supercriticalfluids.

The term “silicate” as used herein refers to any silicon-containingcompound wherein the silicon atom has four bonds to oxygen, wherein atleast one of the oxygen atoms bound to the silicon atom is ionic, suchas any salt of a silicic acid. The counterion to the oxygen ion can beany other suitable ion or ions. An oxygen atom can be substituted withother silicon atoms, allowing for a polymer structure. One or moreoxygen atoms can be double-bonded to the silicon atom; therefore, asilicate molecule can include a silicon atom with 2, 3, or 4 oxygenatoms. Examples of silicates include aluminum silicate. Zeolites are oneexample of materials that can include aluminum silicate. A silicate canbe in the form of a salt or ion.

Herein, when it is designated that a variable in the structure can be “abond,” the variable can represent a direct bond between the two groupsshown as linked to that variable, such as a single bond.

The term “polymer” as used herein can include a copolymer.

Tackifier.

In various embodiments, the present invention provides a tackifiercompound having the structural formula

or a salt thereof. In some embodiments, none of the acid moieties arepresent as a salt, one of the acid moieties is present as a salt, or twoor more of the acid moieties are present as a salt. The salt can haveany suitable counterion, for example, Na⁺, K⁺, Ag⁺, NH₄ ⁺, or multipleacid moieties can share a common ion, such as Al³⁺, Ca²⁺, Cu²⁺, Fe²⁺,Fe³⁺, and Mg²⁺. In some embodiments, the compound is not a salt.

At each occurrence the variable R¹ can be independently selected —OH,—OR³, and

In some embodiments, the variable R¹ can be —OH. In some embodiments,the variable R¹ can be

such as

In some embodiments, the tackifier can have the structure

At each occurrence R′ can be independently chosen from(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene,(C₅-C₂₀(arylene), and (C₁-C₂₀)heteroarylene, wherein R′ can beunsubstituted or substituted with at least one J. In some embodiments,R′ is unsubstituted. The variable R′ can be (C₁-C₅)alkanylene, such as—CH₂—CH₂— (ethanylene) or —CH₂—CH₂—CH₂-(propanylene). The variable R′can be (C₁-C₅)alkylene or (C₂-C₅)alkenylene, such as —CH═CH—(ethenylene). The variable R′ can be (C₅-C₁₀)aryl, such as phenylene,such as ortho-substituted phenylene, or napthyl, such asortho-substituted naphthalene. The variable R′ can be(C₁-C₂₀)heteroaryl.

At each occurrence the variable R² can be independently chosen from —OH,—OR³, —NH₂, —NHR³, and —NR³ ₂. In some embodiments, R² can be —OH. Insome embodiments, R² can be —OR³. At each occurrence R³ can beindependently chosen from (C₁-C₁₀)alkanyl, (C₂-C₁₀)alkenyl,(C₂-C₁₀)alkynyl, C₃-C₂₀(aryl), and (C₁-C₂₀)heteroaryl, wherein R³ isunsubstituted or substituted with at least one J. In some embodiments,the variable R³ can be —OMe.

Fused rings A and B can be each independently chosen from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and n caneach independently be 1-8. Fused rings A and B can be each independentlyunsubstituted or substituted with at least one of J, (C₁-C₁₀)alkenyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy,(C₁-C₁₀)haloalkoxy, (C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl,(C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl, (C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or(C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; wherein each alkyl, alkenyl, alkynyl,haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, andheteroaryl can be independently unsubstituted or further substitutedwith at least one J. The variable J independently at each occurrence canbe chosen from F, Cl, Br, I, OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O),methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R,C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, OC(O)OR,C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R,N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR,N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(C(O)R)C(O)R,N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, and C(═NOR)R, wherein R can beindependently at each occurrence chosen from hydrogen, (C₁-C₁₀)alkyl,(C₁-C₁₀)cycloalkyl, (C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl,(C₁-C₁₀)aralkyl, (C₁-C₁₀)heterocyclyl,(C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl, (C₁-C₁₀)heteroaryl, and(C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein each alkyl, cycloalkyl,cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl,heteroaryl, and heteroarylalkyl is independently unsubstituted orsubstituted with 1-3 J.

In some embodiments, rings A and B are unsubstituted with the exceptionof the ester substituents —OC(O)—R′—C(O)R². In some embodiments, m=n=1,and one of the ester substituents including R′ and R″ is alpha to atleast one carbon atom shared by rings A and B. Rings A and B can be thesame size. Rings A and B can be 5-membered rings. At least one of ringsA and B can include at least one oxygen atom. Each of rings A and B canbe a tetrahydrofuran ring, wherein each carbon atom shared by rings Aand B has an oxygen atom alpha thereto. In some embodiments, m=n. Insome embodiments, m=n=1. Each of each of R′ and the ester substituent—OC(O)—R′—C(O)R² can be alpha to a different carbon atom shared by eachof rings A and B. Rings A and B can form a ring system chosen fromisosorbide, isomannide, and isoidide.

In some embodiments, the tackifier compound is chosen from

In some embodiments, the tackifier compound has the structure

In some embodiments, the tackifier compound has the structure

In some embodiments, the tackifier compound can be chosen from

In some embodiments, the tackifier compound can be chosen from

In some embodiments, the tackifier compound can be chosen from

In some embodiments, the tackifier compound can be chosen from

In some embodiments, the tackifier compound can be chosen from

In some embodiments, the tackifier compound can be chosen from

In some embodiments, the tackifier compound does not include

In some embodiments, the tackifier compound does not include

In some embodiments, the tackifier compound does not include

In some embodiments, the tackifier compound does not include

In some embodiments, the tackifier compound does not include

In some embodiments, the tackifier compound does not include

The tackifier compound can have any suitable solubility characteristics.In some embodiments, by altering the substituents or the length ofvarious portions of the compound, the solubility can be changed suchthat the compound has a solubility that is tuned for a particular use.In some embodiments, the tackifier compound is soluble in organicsolvents. The tackifier compound can be soluble in polar solvents, suchas water, dimethylformamide, and dimethylsulfoxide. The tackifiercompound can be soluble in non-polar solvents, such as hexanes, andbenzene. The tackifier compound can be substantially water soluble. Thetackifier can be substantially insoluble in water. In some embodiments,the tackifier can have a solubility in water of about 0.000,1 g to about0.6 g in about 1 mL of water at about 25° C., or about 0.01 g to about0.3 g dissolve in about 1 mL of water at about 25° C., or about 0.000,1g or less in 1 mL of water, or about 0.005, 0.01, 0.05, 0.1, 0.15, 0.2,0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, or about 0.6 g or more in 1 mL ofwater at 25° C.

The tackifier compound can have any suitable glass transitiontemperature (T_(g)). The glass transition temperature corresponds to atemperature at which the tackifier compound undergoes a reversibletransition from a hard and relatively brittle state into a molten orrubber-like state. The glass transition temperature can be measured inany suitable way, such as via differential scanning calorimetry. In someembodiments, the tackifier compound has a glass transition temperatureof about −90° C. to about 60° C., about −60° C. to about 40° C., orabout −35° C. to about 20° C., or about −90° C. or less, or about −80°C., −70, −60, −50, −40, −30, −20, −10, −5, 0, 5, 10, 15, 20, 25, 30, 40,50° C., or about 60° C. or more.

The tackifier compound can have any suitable tack, which can be measuredin any suitable way, such as by the ASTM 02979 standard, as described inthe Examples. In some embodiments, the tackifier compound has a tack ofabout 50 kPa to about 400 kPa, about 75 kPa to about 250 kPa, 100 kPa toabout 180 kPa, or about 50 kPa or less, or about 60 kPa, 70, 80, 90, 95,100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165,170, 175, 180, 185, 190, 200, 210, 220, 240, 260, 280, 300, 320, 340,360, 380, or about 400 kPa or more, at one or more temperatures that areabout −40° C. to about 80° C., −5° C. to about 55° C., about 5° C. toabout 45° C., about 15° C. to about 35° C., or at about −40° C. or less,or about −35° C., −30, −25, −20, −15, −10, −5, 0, 5, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, 75° C., or about 80° C. or more.

In some embodiments, the tackifier compound has a tack of about 50 kPato about 400 kPa, about 75 kPa to about 250 kPa, 120 kPa to about 140kPa, or about 50 kPa or less, or about 60 kPa, 70, 80, 90, 95, 100, 105,110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175,180, 185, 190, 200, 210, 220, 240, 260, 280, 300, 320, 340, 360, 380, orabout 400 kPa or more, at one or more temperatures that are about 20° C.to about 90° C., 40° C. to about 80° C., or about 50° C. to about 70°C., or about 20° C. or less, or about 25° C., 30, 35, 40, 45, 50, 55,60, 65, 70, 75, 80, 85° C., or about 90° C. or more. In someembodiments, the tackifier compound has a tack of about 200 kPa to about400 kPa, about 250 kPa to about 300 kPa, or about 200 kPa, 205, 210,215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280,285, 290, 295, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, orabout 400 kPa or more at one or more temperatures that are about −40° C.to about 0° C., or about −30° C. to about −10° C., or about −40° C. orless, or about −35° C., −30, −25, −20, −15, −10, −5, or about 0° C. ormore.

Curable Tackifier.

In some embodiments, the present invention provides a cured tackifier ora polymer. The cured tackifier can be any tackifier compound describedherein in a cured state (e.g., a reaction product of a tackifiercompound). For example, the polymer can be a crosslinked tackifiercompound, wherein the tackifier compound is crosslinked any suitable wayand to any suitable degree, such as highly crosslinked. For example, thecurable tackifier compound can include an R′ group having curablemoieties therein or thereon. In some embodiments, at least one R′ caninclude one or more unsaturated aliphatic carbon-carbon bonds, and canbe C₁-C₁₀ alkenylene or C₁-C₁₀ alkynylene. The crosslinking ofunsaturated aliphatic carbon-carbon bonds can occur in any suitable way.The crosslinking can include at least one of application of radiation,application of heat, addition of a chemical crosslinker, or initiationof chemical crosslinking. The crosslinking can be free-radicalpolymerization. The crosslinking can be transition metal-catalyzedpolymerization. In some embodiments, the crosslinking includessubjecting a tackifier that includes —SH moieties thereon to redoxconditions, which can vary the properties in a reversible manner. Insome embodiments, the crosslinking includes subjecting a tackifier thatincludes terminal alkynes and a tackifier that includes terminal azidesto a copper salt-catalyzed polymerization.

Free-radicals can be generated by any suitable method. Free-radicals canbe initiated by, for example, thermal decomposition, photolysis, redoxreactions, persulfates, ionizing radiation, electrolysis, plasma,sonication, or a combination thereof. In one example, a free-radical isgenerated using a free-radical initiator. In one example, thefree-radical initiator can be a free-radical photoinitiator, an organicperoxide, or a free-radical initiator activated by heat. Further, afree-radical photoinitiator can be any free-radical photoinitiatorcapable of initiating cure (cross-linking) of the free-radicalpolymerizable functional groups upon exposure to radiation, for example,having a wavelength of from 200 to 800 nm. In another example, thefree-radical initiator is an organoborane-based free-radical initiator.In one example, the free-radical initiator can be an organic peroxide.For example, elevated temperatures can allow a peroxide to decompose andform a highly reactive radical, which can initiate free-radicalpolymerization. In some examples, decomposed peroxides and theirderivatives can be byproducts. Examples of free-radical initiators caninclude tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid),1,1′-azobis(cyclohexanecarbonitrile), 2,2′-azobisisobutyronitrile AIBN),benzoyl peroxide, 2,2-bis-(tert-butylperoxy)butane,1,1-bis(tert-butylperoxy)cyclohexane,2,5-bis(tert-butylperoxy)-2,6-dimethylhexane,2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,bis(1-(tert-butylperoxy)-1-methylethyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylhydroperoxide, tert-butyl peracetate, tert-butyl peroxybenzoate,tert-butylperoxy isopropyl carbonate, cumene hydroperoxide,cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide,2,4-pentanedione peroxide, peracetic acid, or potassium persulfate. Insome embodiments, the present invention provides a composition includinga free-radical-curable tackifier compound and a free-radical initiator.

A transition metal catalyst can be any suitable transition metalcatalyst. For example, a Ziegler-Natta catalyst, or a Phillips catalyst.

In various embodiments, the polymer can be a reaction product, such as afree-radical polymerization product, of at least one tackifier compoundchosen from

Polymer

In various embodiments, the present invention provides a polymer. Thepolymer can be derived in any suitable way. In some embodiments, thepolymer is a reaction product of a tackifier compound, such as a curedtackifier compound having R′ groups including at least one unsaturatedaliphatic carbon-carbon bond. The reaction product can be a free-radicalpolymerization product. The polymer can have any suitable structurecorresponding to a crosslinked product of any suitable curable tackifiercompound described herein. In various embodiments, the polymer caninclude a repeating unit having the structure

or a salt thereof. Fused rings A and B can be each independently chosenfrom (C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and ncan be each independently 1-8. At each occurrence R⁴ can beindependently selected from —OH, —OR³,

and

At each occurrence R′ can be independently chosen from(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene,C₅-C₂₀(arylene), and (C₁-C₂₀)heteroarylene, wherein R′ can beunsubstituted or substituted with at least one J. At each occurrence R″can be independently a (C₂-C₁₀)alkanylene bonded to at least one of arepeating unit and an end-blocking unit of the polymer at two locations,wherein R″ is unsubstituted or substituted with at least one J. At eachoccurrence R² can be independently chosen from —OH, —OR³, —NH₂, —NHR³,and —NR³ ₂. At each occurrence R³ can be independently chosen from(C₁-C₁₀)alkanyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and(C₁-C₂₀)heteroaryl, wherein R³ is unsubstituted or substituted with atleast one J. Fused rings A and B can be each independently unsubstitutedor substituted with at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl,(C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl can be independently unsubstituted orfurther substituted with at least one J. The variable J independently ateach occurrence is chosen from F, Cl, Br, I, OR, CN, CF₃, OCF₃, R, O, S,C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R, SO₂R,SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R,OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R,N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R can be independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀))cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)heterocyclyl,(C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl, (C₁-C₁₀)heteroaryl, and(C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein each alkyl, cycloalkyl,cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl,heteroaryl, and heteroarylalkyl can be independently unsubstituted orsubstituted with 1-3 J. The polymer can have any suitable molecularweight. For example, the polymer can have a molecular weight of about1,000 g/mol to about 20,000,000 g/mol, about 2,500 g/mol to about10,000,000 g/mol, or about 5,000 g/mol to about 1,000,000 g/mol.

In some embodiments, the repeating unit can have a structure chosen from

At each occurrence L¹ and L² can be independently chosen from a bond and(C₁-C₁₀)alkyl. At each occurrence R⁴ can be independently selected from—OH, —OR³,

In some embodiments, the repeating unit can have the structure

At each occurrence L¹ and L² can be independently chosen from a bond and(C₁-C₁₀)alkyl. At each occurrence R⁴ can be independently selected from—OH, —OR³,

In some embodiments, the repeating unit can have the structure

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl.

In some embodiments, the repeating unit can have a structure chosen from

At each occurrence R⁴ can be independently selected from —OH, —OR³,

In some embodiments, the repeating unit can have the structure

At each occurrence R⁴ can be independently selected from —OH, —OR³,

In some embodiments, the repeating unit can have the structure

In various embodiments, rings A and B, variables m and n, and R″ (whichcorresponds to and can in some embodiments be derived from R′ in thetackifier compound) can be the same or similar. For example, rings A andB can form a ring system chosen from isosorbide, isomannide, andisoidide. The variable R″ can be an alkanylene bonded to at least one ofa repeating unit and an end-blocking unit of the polymer at twolocations and can be chosen from ethylene, propylene, butylene, orpentylene.

In some embodiments, the repeating unit can have a structure chosen from

At each occurrence R⁴ can be independently selected from —OH, —OR³,

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit does not include the structure

In some embodiments, the repeating unit can have the structure

At each occurrence R⁴ can be independently selected from —OH, —OR³,

In some embodiments, the repeating unit can have the structure

In some embodiments, the repeating unit can have a structure chosen from

At each occurrence R⁴ can be independently selected from —OH, —OR³,

In some embodiments, the repeating unit can have a structure chosen from

At each occurrence R⁴ can be independently selected from —OH, —OR³,

In some embodiments, the repeating unit can have a structure chosen from

Method of Using Tackifier.

In various embodiments, the present invention provides a method of usinga tackifier compound. The tackifier compound can be any suitabletackifier compound described herein, such as a compound having thestructure

or the salt thereof. The tackifier compound can be used in any suitableway. The method can include contacting the tackifier compound to a firstsubstrate. The tackifier compound can be contacted neat or in acomposition. The contacting can be any suitable contacting, wherein thetackifier compound and the first substrate at least partially come intocontact, such that the tackifier is bonded to the first substrate. Thebonding can be any suitable bonding, for example, such that thetackifier compound has greater adhesion to the first substrate than anon-tackifier compound contacted under corresponding conditions. Thefirst substrate can be any suitable material.

The method can further include contacting the tackifier compound to asecond substrate. The contacting of the tackifier compound to the secondsubstrate can be any suitable contacting, such that the tackifiercompound and the second substrate at least partially conic into contact,such that the tackifier compound is bonded to the second substrate andsuch that the first substrate is bonded to the second substrate at leastpartially via the tackifier compound. The bonding between the tackifierand the second substrate can be any suitable bonding, for example, suchthat the tackifier compound has greater adhesion to the second substratethan a non-tackifier compound contacted under corresponding conditions.The second substrate can be any suitable material. The bonding betweenthe first substrate and the second substrate via the tackifier compoundcan be any suitable bonding, for example, such that the first substrateand the second substrate have greater adhesion than the first substrateand the second substrate would have under corresponding conditionswithout the presence of the tackifier compound therebetween.

In some embodiments, at least one R′ is C₁-C₁₀ alkenylene or C₁-C₁₀alkynylene, and the method further includes crosslinking the tackifiercompound to provide a polymer. The polymer can be any suitable polymerdescribed herein, such as a polymer including a repeating unit havingthe structure

or a salt thereof. At each occurrence R″ can be independently a(C₂-C₁₀)alkanylene bonded to at least one of a repeating unit and anend-blocking unit of the polymer at two locations, wherein R″ isunsubstituted or substituted with at least one J. The crosslinking caninclude any suitable crosslinking, such as at least one of applicationof heat, application of radiation, addition of a chemical crosslinker,and initiation of a chemical crosslinker. In some embodiments, thechemical crosslinker includes a suitable free-radical initiator, such asany free-radical initiator described herein.Method of Making Tackifier.

In various embodiments, the present invention provides a method ofmaking a tackifier compound. The method includes contacting a compoundhaving the structure

and an acid anhydride having the structure

to provide a tackifier compound. The tackifier compound can be anytackifier compound described herein, such as a compound having thestructure

or a salt thereof. The fused rings A and B can each independently bechosen from (C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables mand n can be each independently 1-8. At each occurrence R¹ can beindependently selected from —OH, —OR³, and

At each occurrence R′ can be independently chosen from(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene,C₅-C₁₀(arylene), and (C₁-C₂₀)heteroarylene, wherein R′ can beunsubstituted or substituted with at least one J. At each occurrence R²can be independently chosen from —OH, —OR³, —NH₂, —NHR³, and —NR³ ₂. Ateach occurrence R³ can be independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ can be unsubstituted or substituted with at least one J.Fused rings A and B can be each independently unsubstituted orsubstituted with at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl,(C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J. The variable J independently ateach occurrence can be chosen from F, Cl, Br, I, OR, CN, CF₃, OCF₃, R,O, S, C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R, SO₂R,SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R,OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R,N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R can be independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl can be independentlyunsubstituted or substituted with 1-3 J.

Rings A and B can form any suitable fused ring system. In someembodiments, m=n=1. In various embodiments, the polyol can be derived atleast in part from renewable (e.g., non-petroleum) sources.Advantageously, by deriving the polyol from renewable sources, theresulting tackifier can be at least in part derived from renewablesources. For example, in some embodiments the polyol can be isosorbide:

In some embodiments the polyol can be isomannide:

In some embodiments the polyol can be isoidide:

Isosorbide is a natural diol that can be derived from corn. Isosorbide,isomannide, and isoidide are three isomers of 1,4:3,6-dianhydrohexitol,and can be derived from, for example, D-glucose, D-mannose, andL-fructose, respectively. Isosorbide is the most widely available of thethree isomers, as a by-product of the starch industry. Isosorbide,isomannide, and isoidide have characteristics including rigidity,thermal stability, chirality, and lack of toxicity, which make thesepolyols highly desirable for use in synthesizing environmentally benignand useful tackifiers therefrom.

The anhydride can be any suitable cyclic anhydride. For example, theanhydride can be chosen from succinic anhydride (e.g., R′=ethylene),glutaric anhydride (e.g., R′=propylene), and maleic anhydride (e.g.,R′=ethenylene). In some examples, the anhydride can be derived at leastin part from renewable sources. Advantageously, by deriving theanhydride from renewable sources, the resulting tackifier compound canbe at least in part derived from renewable sources; if the polyol isalso renewably derived, an even larger proportion of the tackifiercompound is renewably derived. In various embodiments, the anhydride canbe succinic anhydride, which can be derived from succinic acid, whichcan be isolated from, for example, the products of sugar fermentation.

The contacting of the fused bicyclic polyol and the acid anhydride canbe performed under any suitable conditions. In some examples, theanhydride can be used in excess, such as about 1.2 equivalents or less,about 1.4 equivalents, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or about 3.0or more equivalents, with about 1 equivalent of bicyclic polyol. Thereaction can be performed neat, or with any suitable solvent and usingany suitable concentration. The reaction can be stirred or unstirred.The reaction can be cooled, unheated, heated, or any combinationthereof. The reaction can be cooled such that the temperature of thereaction does not exceed about −20° C. or less, about −10° C., −5° C.,0° C., 5° C., 10° C., or about 20° C. or more. The reaction can beunheated. The reaction can be heated to any suitable temperature, forexample, about 80° C. or less, about 90° C., 100, 110, 120, 130, 140,150, 180, 200, 220, 240, 260, 280, or about 300° C. or higher. In someexamples, substantially all of the reaction vessel can be heated, forexample, to avoid sublimation of the anhydride. The cooling, no heating,or heating can be performed for any suitable time, for example, about 10min or less, about 30 min, 1 h, 2 h, 4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d,2 d, or about 3 d or more. The resulting polyacid tackifier can becarried forward to the next step crude or can be purified by anysuitable technique. In some examples, the resulting crude polyacid issufficiently pure such that little or no purification is required. Forexample, the crude tackifier can be ready for use as a tackifiercompound as-is with no additional purification. In some embodiments, anysolvent can be evaporated using standard techniques such as a rotatingevaporator, and vacuum distillation or chromatography can be used topurify the polyacid.

In some embodiments, the contacting can further including contacting thereaction mixture including the cyclic anhydride and the polyol with asuitable amount of a catalyst. The catalyst can be any suitablecatalyst. In some embodiments, the catalyst is an acid, such as aBronsted acid (e.g., mineral acids such as HCl, H₂SO₄, HF, HBr, ororganic acids such as any (C₁-C₃₀)alkanoic or alkenoic acid such asacetic or formic acid) or a Lewis acid (e.g., a metal halide, such asAlCl₃, AlBr₃, BF₃, FeBr₃, FeCl₃, SnCl₄, SiF₄, TiCl₄, and the like). Insome embodiments, as compared to the method performed without thecatalyst, the catalyst can reduce the reaction time needed to run thereaction to completion, reduce the reaction temperature needed toachieve a given reaction rate, and can allow production of the tackifiercompound for a lower overall cost.

The method can further include synthesizing esterification or amidationproducts of the polyacid. The esterification products can be synthesizedin any suitable fashion; for example, contacting with a base in thepresence of an alkyl halide to generate the corresponding alkyl ester.Amidation products can be synthesized in any suitable fashion, forexample, transformation of the polyacid to the acyl halide followed byamidation.

In some embodiments, the method of making the tackifier compound can bea method of making a polymer, and can further include crosslinking thetackifier compound. The crosslinking can be any suitable crosslinking,such as free-radical crosslinking. The tackifier compound can have R′that includes a crosslinkable group; for example, R′ can be(C₂-C₁₀)alkenylene or (C₂-C₁₀)alkynylene. The polymer can be anysuitable polymer described herein, such as a polymer including arepeating unit having the structure

or a salt thereof.

The crosslinking can be performed in any suitable manner. For example,the crosslinking can include heating the tackifier compound to about 80°C. or less, about 90° C., 100, 110, 120, 130, 140, 150, 160, 170, 180,190, 200, 210, 220, 230, 240, 250, 260, 280, or about 300° C. or higher.The heating can occur for any suitable duration such that crosslinkingoccurs, for example, about 10 min or less, about 30 min, 1 h, 2 h, 4 h,6 h, 12 h, 18 h, 24 h, 1.5 d, 2 d, or about 3 d or more. In someembodiments, the crosslinking can occur at room temperature or near roomtemperature and can include mixing a crosslinker compound with thetackifier compound and allowing suitable time to pass for thecrosslinking to occur, such as about 10 min or less, about 30 min, 1 h,2 h, 4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d, 2 d, or about 3 d or more. Insome examples, the crosslinker compound can be a suitable free-radicalinitiator, such as any free-radical initiator described herein. A methodof crosslinking including heating can optionally include the presence ofone or more suitable crosslinker compounds. In some embodiments, thecrosslinking can include exposing the tackifier compound to a suitableform of radiation of a suitable intensity and for a suitable duration.

System Including Tackifier or Cured Tackifier.

In various embodiments, the present invention provides a systemincluding a tackifier compound. The tackifier compound can be anysuitable tackifier compound described herein, such as a tackifiercompound having the structural formula

or a salt thereof. The tackifier compound can be neat or in acomposition. In the system, the tackifier compound is bonded to thefirst substrate. The first substrate can be any suitable material. Thebonding can be any suitable bonding, for example, such that thetackifier compound has greater adhesion to the first substrate than anon-tackifier compound (e.g., water) contacting the first substrateunder corresponding conditions. In some embodiments, the system furtherincludes a second substrate. The tackifier compound can be bonded to thefirst and second substrate such as to bond the first substrate to thesecond substrate at least partially via the tackifier compound. Thesecond substrate can be any suitable material. The bonding between thesecond substrate and the tackifier compound can be any suitable bonding,for example, such that the tackifier compound and the second substratehave greater adhesion than a non-tackifier compound contacting thesecond substrate under corresponding conditions. The bonding between thefirst substrate and the second substrate can be any suitable bonding,for example, such that the first substrate and the second substrate havegreater adhesion than the first substrate and the second substrate wouldhave under corresponding conditions without the presence of thetackifier compound therebetween.

In various embodiments, the present invention provides a systemincluding a polymer. The polymer can be any suitable polymer describedherein, such as a polymer including a repeating unit having thestructure

or a salt thereof. The polymer can be neat or in a composition. In thesystem, the polymer is bonded to the first substrate. The firstsubstrate can be any suitable material. The bonding can be any suitablebonding, for example, such that the polymer has greater adhesion to thefirst substrate than a non-tackifier compound contacting the firstsubstrate under corresponding conditions. In some embodiments, thesystem further includes a second substrate. The polymer can be bonded tothe first and second substrate such as to bond the first substrate tothe second substrate at least partially via the polymer. The secondsubstrate can be any suitable material. The bonding between the secondsubstrate and the polymer can be any suitable bonding, for example, suchthat the polymer and the second substrate have greater adhesion than anon-tackifier compound contacting the second substrate undercorresponding conditions. The bonding between the first substrate andthe second substrate can be any suitable bonding, for example, such thatthe first substrate and the second substrate have greater adhesion thanthe first substrate and the second substrate would have undercorresponding conditions without the presence of the polymer compoundtherebetween.

EXAMPLES

The present invention can be better understood by reference to thefollowing Examples which are offered by way of illustration. The presentinvention is not limited to the Examples given herein.

Example 1a. Synthesis of Tackifiers 3a-3c from Isosorbide 1

A mixture of isosorbide (1, 7.31 g, 50 mmol) and succinic anhydride (2a,11.51 g, 115 mmol, 2.3 equiv) was heated at 120° C. for 24 hr to givediacid 3a as a viscous orange oil. To avoid sublimation of succinicanhydride 2a, the entire reaction vessel was heated. The chemical yieldwas estimated by ¹H NMR analysis to be approximately 100%. Sublimationof succinic anhydride (2a) from the crude material afforded a sample ofdiacid 3a for analysis. 3a: R_(f)=0.43 (silica gel, EtOAc); [α]_(D)²³=+90.9° (c=1.00, CHCl₃); IR (thin film): ν_(max)=1739, 1716 cm⁻¹; ¹HNMR (400 MHz, CDCl₃): δ=10.51 (br, 2H), 5.21 (s, 1H), 5.17 (q, J=5.4 Hz,1H), 4.83 (t, J=5.1 Hz, 1H), 4.47 (d, J=4.7, 1H), 3.94 (m, 3H), 3.81(dd, J=10.0, 5.1 Hz, 1H), 2.69 (s, 4H), 2.65 (m, 4H); ¹³C NMR (100 MHz,CDCl₃): δ=178.01, 177.95, 171.71, 171.33, 85.88, 80.87, 78.37, 74.42,73.33, 70.54, 29.04, 29.01, 28.98, 28.76 ppm; HRMS (ESI-QTOF) calcd forC₁₄H₁₇O₁₀ ⁺ [M−H⁺]: 345.0822, found: 345.0827.

A mixture of isosorbide (1, 7.31 g, 50 mmol) and glutaric anhydride (2b,14.26 g, 125 mmol, 2.5 equiv) was refluxed at 170° C. for 24 hr to givediacid 3b as a black viscous liquid. The chemical yield was estimated byNMR analysis to be approximately 92%. Evaporation of glutaric anhydride(2b) from the crude material followed by chromatography in 0.5%methanol/99.5% ethyl acetate afforded a sample of diacid as a cleartransparent oil 3b for analysis. 3b: R_(f)=0.35 (silica gel, EtOAc);[α]_(D) ²³=+112.74° (c=1.00, CHCl₃); IR (thin film): ν_(max)=3514, 1736cm⁻¹; ¹H NMR (600 MHz, CDCl₃): δ=5.19 (s, 1H), 5.16 (q, J=5.5 Hz, 1H),4.84 (t, J=4.7 Hz, 1H), 4.47 (d, J=4.3 Hz, 1H), 3.96 (d, J=3.5 Hz, 2H),3.93 (dd, J=10.1, 6.1 Hz, 1H), 3.81 (dd, J=10.0, 5.1 Hz, 1H), 2.47 (t,J=6.7 Hz, 4H) 2.45-2.38 (m, 4H), 2.01-1.91 (m, 4H) ppm; ¹³C NMR (151MHz, CDCl₃): δ=178.65, 178.50, 172.40, 172.07, 85.99, 80.79, 78.19,74.14, 73.42, 70.55, 33.21, 32.99, 32.94, 32.85, 19.92, 19.81 ppm; HRMS(ESI-QTOF) calcd for C₁₆H₂₂O₁₀Na⁺ [M+Na⁺]: 397.1105, found: 397.1109;DSC (He, 10° C. min⁻¹): T_(g)=−26° C., T_(m)=31° C.

A mixture of isosorbide (1, 4.38 g, 30 mmol) and maleic anhydride (2c,7.35 g, 75 mmol, 2.5 equiv) was heated at 170° C. for 72 hr to givediacid 3c as a yellow solid. To avoid sublimation of maleic anhydride2c, the entire reaction vessel was heated. The chemical yield wasestimated by ¹H. NMR analysis to be approximately 73%. 3c: R_(f)=0.27(silica gel, 30% MeOH/70% EtOAc); IR (thin film): ν_(max)=3527, 1644cm⁻¹; NMR (400 MHz, DMSO-d⁶): δ=13.24 (br, 2H), 6.87-6.64 (m, 4H), 5.24(m, 1H), 5.19 (m, 1H), 4.87 (m, 1H), 4.51 (m, 1H), 3.99-3.92 (m, 1H),3.92-3.81 (m, 3H) ppm; HRMS (ESI-QTOF) calcd for C₁₄H₁₃O₁₀ ⁻ [M−H⁺]:341.0514, found: 341.0524; DSC (He, 10° C. min⁻¹): T_(g)=20° C.,T_(m)=158° C.

Example 1b. Synthesis of Tackifiers 5a-5c from Isomannide 4(Hypothetical for 5c Only

A mixture of isomannide (4, 7.31 g, 50 mmol) and succinic anhydride (2a,11.51 g, 115 mmol, 2.3 equiv) was heated at 120° C. for 24 h to givediacid 5a as a viscous orange oil. The entire reaction vessel was heatedto minimize evaporative loss of succinic anhydride (2a). Vacuumsublimation of succinic anhydride (2a) from the crude material gave asample of diacid 5a for analysis. 5a: R_(f)=0.38 (silica gel, EtOAc);[α]_(D) ²³=+116.9 (c=1.00, CHCl₃); IR (thin film): ν_(max)=1741, 1717cm⁻¹; ¹H NMR (400 MHz, CDCl₃): δ=8.29 (br, 2H), 5.10 (d, J=5.8 Hz, 2H),4.68 (dd, J=9.3, 3.8 Hz, 2H), 4.01 (dd, J=9.6, 6.1 Hz, 2H), 3.79 (dd,J=9.6, 6.3 Hz, 2H), 2.77-2.70 (m, 4H), 2.70-2.65 (m, 4H) ppm; ¹³C NMR(100 MHz, CDCl₃): δ=178.20, 171.37, 80.58, 73.98, 70.72, 29.40, 29.25ppm; HRMS (ESI-QTOF) calcd for C₁₄H₁₇O₁₀ ⁻ [M−H⁺]: 345.0822, found:345.0821; DSC (He, 10° C. min⁻¹): T_(g)=−2° C.

A mixture of isomannide (4, 7.31 g, 50 mmol) and glutaric anhydride (2b,14.26 g, 125 mmol, 2.5 equiv) was refluxed at 170° C. for 24 hr to givediacid 5b as a black viscous liquid. The chemical yield was estimated by¹H NMR analysis to be approximately 91%. Evaporation of glutaricanhydride (2b) from the crude material followed by chromatography in0.5% methanol/99.5% ethyl acetate afforded a sample of diacid 5b as aclear transparent oil for analysis. 5b: R_(f)=0.35 (silica gel, EtOAc);[α]_(D) ²³=+87.28°; (c=1.00, CHCl₃); IR (thin film): ν_(max)=3422, 1736,1709 cm⁻¹; ¹H NMR (600 MHz, CDCl₃): δ=5.09 (q, J=5.5 Hz, 2H), 4.70 (d,J=4.2 Hz, 2H), 4.02. (dd, J=9.4, 6.3 Hz, 2H), 3.81 (dd, J=9.4, 6.7 Hz,2H), 2.49 (dt, J=7.3, 3.6, Hz, 4H), 2.46 (t, J=7.1 Hz, 4H), 1.99 (p,J=7.2 Hz, 4H) ppm; ¹³C NMR (151 MHz, CDCl₃): δ=178.97, 172.42, 80.50,73.77, 70.69, 32.96, 32.90, 19.93 ppm; C₁₆H₂₂O₁₀Na⁺ [M+Na⁺]: 397.1105,found: 397.1112; DSC (He, 10° C. min⁻¹): T_(g)=26° C., T_(m)=33° C.

The procedure of Example 1a is followed using isomannide in place ofisosorbide to give diacid 5c at about 100% yield at high purity.

Example 1c. Synthesis of Tackifiers 7a-7c from Isoidide 6 (Hypothetical)

The procedure of Example 1a is followed using isoidide in place ofisosorbide to give diacids 7a-7c at about 100% yield at high purity.

Example 1d. Synthesis of Tackifier 8 from Diacid 3a

A mixture of diacid 3a (7.27 g, 21 mmol), methyl iodide (4 mL, 63 mmol,3 eq.), and potassium carbonate (8.71 g, 63 mmol, 3 eq.) were dissolvedin N,N-dimethylformamide (42 mL), and heating to 35° C. for 24 hr togive crude dimethyl ester 8. The reaction was diluted with 80 mL ofwater and extracted with 2×50 mL EtOAc followed by washing with 3>100 mLH₂O and 1×100 mL brine and dried over MgSO₄. Purification viachromatography in 60% ethyl acetate/40% hexanes resulted in puredimethyl ester as a clear viscous oil in 40% yield. 8: R_(f)=0.36(silica gel, 60% EtOAc/40% Hexanes); [α]_(D) ²³=+28.69° (c=1.00, CHCl₃);IR (thin film): ν_(max)=1739 cm⁻¹; ¹H NMR (600 MHz, CDCl₃): δ=5.20 (s,1H), 5.16 (q, J=5.6 Hz, 1H), 4.81 (t, J=5.0 Hz, 1H), 4.47 (d, J=4.7 Hz,1H), 3.96 (d, J=2.3 Hz, 2H), 3.92 (dd, J=9.9, 6.0 Hz, 1H), 3.80 (dd,J=9.9, 5.2 Hz, 1H), 3.69 (s, 3H), 3.68 (s, 3H) 2.71-2.59 (m, 8H) ppm;¹³C NMR (151 MHz, CDCl₃): δ=172.66, 172.63, 171.79, 171.49, 85.97,80.85, 78.37, 74.32, 73.40, 70.50, 52.04, 52.02, 29.18, 28.95, 28.93,28.88 ppm; HRMS (ESI-QTOF) calcd for C₁₆H₂₃O₁₀ ⁺ [M+H⁺]: 375.1286,found: 375.1292; DSC (He, 10° C. min⁻¹); T_(g)=−34° C., T_(m)=29° C.

Example 2. Properties of the Tackifiers of Example 1a

Although none of the precursors 1 and 2a-2c had significant tackiness,the resultant diacids (3a-3c) were highly tacky (see Table 1). Alteringthe identity of the acid anhydride altered tackifier properties. Forexample, succinic anhydride-derived tackifier 3a was substantiallywater-soluble and could be cleanly washed away by water, yet it remainedactive as a tackifier under damp conditions. In contrast, glutaricanhydride-derived tackifier 3b, differing from 3a in the addition of aCH₂ moiety to the cyclic anhydride component, was substantiallywater-insoluble. Changes to the anhydride component also resulted indifferences in the glass transition temperature (T_(g)) and in thetemperature range over which the maximum degree of tackiness wasobserved.

Tack was measured by modifications to the ASTM 02979 standard. On anInstron® load frame, the tackifier to be tested was applied to a glassslide at a thickness of 0.1 mm. The slide was then clamped to a flatsurface and, perpendicularly, a type 304 stainless steel probe measuring5 mm in diameter, with a 90° polished tip was place above the slide. Theprobe was then lowered at a rate of 0.5 mm sec⁻¹ and contacted thesurface at an average force of 1.5 N. The probe was then held on thesurface for 1.0 sec and then raised at a rate of 0.5 mm sec⁻¹. Tack wasmeasured as the maximum force required to remove the probe from thesurface of the tackifier. T_(g) was measured by DSC.

TABLE 1 Properties of tackifiers at selected temperatures from −50° C.to 80° C. Water soluble? T_(g) (° C.) T_(m) (° C.) Maximum tack (kPa) 3aY −2 168 at 25° C. 3b N −24 31 112 at 25° C. 3c N 16 158 130 at 60° C.5a Y −2 121 at 25° C. 5b N −26 33 107 at 60° C. 8 Y −34 29 285 at −20°C.  

Example 3. Curing of Tackifier 3c

The alkene in maleic anhydride-derived tackifier 3c in Example 1a wassubjected to a curing process to generate a cross-linked polymer. Whenheated to about 200° C., a closed-ended borosilicate glass tube thatcould be readily removed from the substance prior to curing was stuck inplace after the curing; rather than come free, the glass tube sheared atthe surface of the cured material. Thus, the material cured to yield ahard substance that held in place a piece of glass with substantialstrength and permanence.

The terms and expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by specificembodiments and optional features, modification and variation of theconcepts herein disclosed may be resorted to by those of ordinary skillin the art, and that such modifications and variations are considered tobe within the scope of this invention as defined by the appended claims.

ADDITIONAL EMBODIMENTS

The present invention provides for the following exemplary embodiments,the numbering of which is not to be construed as designating levels ofimportance:

Embodiment 1 provides a tackifier compound having the structural formula

or a salt thereof;

wherein fused rings A and B are each independently chosen from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl;

m and n are each independently 1-8;

at each occurrence R¹ is independently selected from —OH, —OR³, and

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J;

at each occurrence R² is independently chosen from —OH, —OR³, —NH₂,—NHR³, and —NR³ ₂;

at each occurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J;

fused rings A and B are each independently unsubstituted or substitutedwith at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and

wherein J independently at each occurrence is chosen from F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₃C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

Embodiment 2 provides the tackifier compound of Embodiment 1, whereinthe compound is not a salt.

Embodiment 3 provides the tackifier compound of any one of Embodiments1-2, wherein the compound is substantially water soluble.

Embodiment 4 provides the tackifier compound of any one of Embodiments1-3, wherein the compound is partially soluble in water, such that about0.000,1 g to about 0.6 g dissolve in about 1 mL of water at about 25° C.

Embodiment 5 provides the tackifier compound of any one of Embodiments1-4, wherein the compound is partially soluble in water, such that about0.01 g to about 0.3 g dissolve in about 1 mL of water at about 25° C.

Embodiment 6 provides the tackifier compound of any one of Embodiments1-5, wherein the compound is substantially insoluble in water.

Embodiment 7 provides the tackifier compound of any one of Embodiments1-6, wherein the compound has a glass transition temperature of about−90° C. to about 60° C.

Embodiment 8 provides the tackifier compound of any one of Embodiments1-7, wherein the compound has a glass transition temperature of about−60° C. to about 40° C.

Embodiment 9 provides the tackifier compound of any one of Embodiments1-8, wherein the compound has a glass transition temperature of about−35° C. to about 20° C.

Embodiment 10 provides the tackifier compound of any one of Embodiments1-9, wherein the compound has a tack of about 50 kPa to about 400 kPa atone or more temperatures that are about −40° C. to about 80° C.

Embodiment 11 provides the tackifier compound of any one of Embodiments1-10, wherein the compound has a tack of about 50 kPa to about 400 kPaat one or more temperatures that are about 5° C. to about 45° C.

Embodiment 12 provides the tackifier compound of any one of Embodiments1-11, wherein the compound has a tack of about 50 kPa to about 400 kPaat one or more temperatures that are about 40° C. to about 80° C.

Embodiment 13 provides the tackifier compound of any one of Embodiments1-12, wherein the compound has a tack of about 75 kPa to about 250 kPaat one or more temperatures that are about 15° C. to about 35° C.

Embodiment 14 provides the tackifier compound of any one of Embodiments1-13, wherein the compound has a tack of about 75 kPa to about 250 kPaat one or more temperatures that are about 50° C. to about 70° C.

Embodiment 15 provides the tackifier compound of any one of Embodiments1-14, wherein the compound has a tack of about 100 kPa to about 180 kPaat one or more temperatures that are about 15° C. to about 35° C.

Embodiment 16 provides the tackifier compound of any one of Embodiments1-15, wherein the compound has a tack of about 120 kPa to about 140 kPaat one or more temperatures that are about 50° C. to about 70° C.

Embodiment 17 provides the tackifier compound of any one of Embodiments1-16, wherein the compound has a tack of about 200 kPa to about 400 kPaat one or more temperatures that are about −40° C. to about 0° C.

Embodiment 18 provides the tackifier compound of any one of Embodiments1-17, wherein one —C(O)OH moiety is in the form of a salt.

Embodiment 19 provides the tackifier compound of any one of Embodiments1-18, wherein two —C(O)OH moieties are in the form of a salt.

Embodiment 20 provides the tackifier compound of any one of Embodiments1-19, wherein the salt comprises at least one counterion chosen fromNa⁺, K⁺, Ag⁺, NH₄ ⁺, Ca²⁺, Cu²⁺, Fe³⁺, and Mg²⁺.

Embodiment 21 provides the tackifier compound of any one of Embodiments1-20, wherein R′ is —OH.

Embodiment 22 provides the tackifier compound of any one of Embodiments1-21, wherein R¹ is

Embodiment 23 provides the tackifier compound of any one of Embodiments1-22, wherein R² is —OH.

Embodiment 24 provides the tackifier compound of any one of Embodiments1-23, wherein the compound has the structure

Embodiment 25 provides the tackifier compound of any one of Embodiments1-24, wherein R² is —OR³.

Embodiment 26 provides the tackifier compound of Embodiment 25, whereinR³ is —O(C₁-C₅)alkyl.

Embodiment 27 provides the tackifier compound of any one of Embodiments25-26, wherein R³ is —OMe.

Embodiment 28 provides the tackifier compound of any one of Embodiments1-27, wherein at each occurrence R′ is independently unsubstituted.

Embodiment 29 provides the tackifier compound of any one of Embodiments1-28, wherein at each occurrence R′ is independently (C₁-C₅)alkylene,(C₅-C₁₀)aryl, or (C₂-C₅)alkenylene.

Embodiment 30 provides the tackifier compound of any one of Embodiments1-29, wherein at each occurrence R′ is independently —CH₂—CH₂—,—CH₂—CH₂—CH₂—, o-phenylene, or CH═CH—.

Embodiment 31 provides the tackifier compound of any one of Embodiments1-30, wherein rings A and B are unsubstituted with the exception of theone or more ester substituents —OC(O)—R′—C(O)R².

Embodiment 32 provides the tackifier compound of any one of Embodiments1-31, wherein m=n=1, and one of the ester substituents including R′ andR″ is alpha to at least one carbon atom shared by rings A and B.

Embodiment 33 provides the tackifier compound of any one of Embodiments1-32, wherein rings A and B are the same size.

Embodiment 34 provides the tackifier compound of any one of Embodiments1-33, wherein rings A and B are 5-membered rings.

Embodiment 35 provides the tackifier compound of any one of Embodiments1-34, wherein at least one of rings A and B include at least one oxygenatom.

Embodiment 36 provides the tackifier compound of any one of Embodiments1-35, wherein each of rings A and B is a tetrahydrofuran ring, whereineach carbon atom shared by rings A and B has an oxygen atom alphathereto.

Embodiment 37 provides the tackifier compound of any one of Embodiments1-36, wherein m=n.

Embodiment 38 provides the tackifier compound of any one of Embodiments1-37, wherein m=n=1.

Embodiment 39 provides the tackifier compound of Embodiment 38, whereineach of R¹ and the ester substituent —OC(O)—R′—C(O)R² are alpha to adifferent carbon atom shared by each of rings A and B.

Embodiment 40 provides the tackifier compound of any one of Embodiments1-39, wherein rings A and B form a ring system chosen from isosorbide,isomannide, and isoidide.

Embodiment 41 provides the tackifier compound of any one of Embodiments1-40, wherein rings A and B are unsubstituted.

Embodiment 42 provides the tackifier compound of any one of Embodiments1-41, wherein the compound is chosen from

Embodiment 43 provides the tackifier compound of any one of Embodiments1-42, wherein the compound is

Embodiment 44 provides the tackifier compound of any one of Embodiments1-43, wherein the compound is

Embodiment 45 provides the tackifier compound of any one of Embodiments1-44, wherein the compound is chosen from

Embodiment 46 provides the tackifier compound of any one of Embodiments1-45, wherein the compound is chosen from

Embodiment 47 provides the tackifier compound of any one of Embodiments1-46, wherein the compound is chosen from

Embodiment 48 provides the tackifier compound of any one of Embodiments1-47, wherein the compound is chosen from

Embodiment 49 provides the tackifier compound of any one of Embodiments1-48, wherein the compound is chosen from

Embodiment 50 provides the tackifier compound of any one of Embodiments1-49, wherein the compound is chosen from

Embodiment 51 provides the tackifier compound of any one of Embodiments1-50, wherein at least one R′ is C₁-C₁₀ alkenylene or C₁-C₁₀ alkynylene.

Embodiment 52 provides a reaction product of the tackifier compound ofEmbodiment 51.

Embodiment 53 provides a composition comprising the tackifier compoundof Embodiment 51 and a free-radical initiator or a transition metalcatalyst.

Embodiment 54 provides the composition of Embodiment 53, wherein thefree-radical initiator is chosen from tert-amyl peroxybenzoate,4,4-azobis(4-cyanovaleric acid), 1,1′-azobis(cyclohexanecarbonitrile),2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide,2,2-bis-(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane,2,5-bis(tert-butylperoxy)-2,6-dimethylhexane,2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,bis(1-(tert-butylperoxy)-1-methylethyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylhydroperoxide, tert-butyl peracetate, tert-butyl peroxybenzoate,tert-butylperoxy isopropyl carbonate, cumene hydroperoxide,cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide,2,4-pentanedione peroxide, peracetic acid, and potassium persulfate, orwherein the transition metal catalyst is a Ziegler-Natta catalyst or aPhillips catalyst.

Embodiment 55 provides the tackifier compound of any one of Embodiments1-51, wherein the compound is chosen from

Embodiment 56 provides a reaction product of the tackifier compound ofEmbodiment 55.

Embodiment 57 provides the reaction product of Embodiment 56, whereinthe reaction product is a cured product.

Embodiment 58 provides the reaction product of any one of Embodiments56-57, wherein the reaction product is at least one of a free-radicalpolymerization product and a transition metal-catalyzed polymerizationproduct.

Embodiment 59 provides a polymer comprising a repeating unit having thestructure

or a salt thereof;

wherein fused rings A and B are each independently chosen from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl;

m and n are each independently 1-8;

each occurrence R⁴ is independently selected from —OH, —OR³,

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J;

at each occurrence R″ is independently a (C₂-C₁₀)alkanylene bonded to atleast one of a repeating unit and an end-blocking unit of the polymer attwo locations, wherein R″ is unsubstituted or substituted with at leastone J;

at each occurrence R² is independently chosen from —OH, —OR³, —NH₂,—NHR³, and —NR³ ₂;

at each occurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J;

fused rings A and B are each independently unsubstituted or substitutedwith at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and

wherein J independently at each occurrence is chosen from F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

Embodiment 60 provides the polymer of Embodiment 59, wherein therepeating unit has a structure chosen from

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl, and wherein at each occurrence R⁴ isindependently selected from —OH, —OR³,

Embodiment 61 provides the polymer of any one of Embodiments 59-60,wherein the repeating unit has the structure

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl, and wherein at each occurrence R⁴ isindependently selected from —OH, —OR³,

Embodiment 62 provides the polymer of any one of Embodiments 59-61,wherein the repeating unit has the structure

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl.

Embodiment 63 provides the polymer of any one of Embodiments 59-62,wherein the repeating unit has a structure chosen from

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

Embodiment 64 provides the polymer of any one of Embodiments 59-63,wherein the repeating unit has the structure

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

Embodiment 65 provides the polymer of any one of Embodiments 59-64,wherein the repeating unit has the structure

Embodiment 66 provides the polymer of any one of Embodiments 59-65,wherein rings A and B form a ring system chosen from isosorbide,isomannide, and isoidide.

Embodiment 67 provides the polymer of any one of Embodiments 59-66,wherein R″ is an alkanylene bonded to at least one of a repeating unitand an end-blocking unit of the polymer at two locations and is chosenfrom ethylene, propylene, butylene, or pentylene.

Embodiment 68 provides the polymer of any one of Embodiments 59-67,wherein the repeating unit has a structure chosen from

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

Embodiment 69 provides the polymer of any one of Embodiments 59-68,wherein the repeating unit has the structure

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

Embodiment 70 provides the polymer of any one of Embodiments 59-69,wherein the repeating unit has the structure

Embodiment 71 provides the polymer of any one of Embodiments 59-70,wherein the repeating unit has a structure chosen from

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

Embodiment 72 provides the polymer of any one of Embodiments 59-71,wherein the repeating unit has a structure chosen from

wherein at each occurrence R⁴ is independently selected front —OH, —OR³,

Embodiment 73 provides the polymer of any one of Embodiments 59-72,wherein the repeating unit has a structure chosen from

Embodiment 74 provides a system comprising:

a tackifier compound having the structural formula

or a salt thereof;

wherein fused rings A and B are each independently chosen from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl;

m and n are each independently 1-8;

at each occurrence R¹ is independently selected from —OH, —OR³, and

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J;

at each occurrence R² is independently chosen from —OH, —OR³, —NH₂,—NHR³, and —NR³ ₂;

at each occurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₃-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J;

fused rings A and B are each independently unsubstituted or substitutedwith at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₀-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and

wherein J independently at each occurrence is chosen from F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J; and

a first substrate;

wherein the tackifier compound is bonded to the first substrate.

Embodiment 75 provides the system of Embodiment 74, further comprising asecond substrate, wherein the tackifier compound is bonded to the firstand second substrate such as to bond the first substrate to the secondsubstrate at least partially via the tackifier compound.

Embodiment 76 provides a system comprising:

a polymer comprising a repeating unit having the structure

or a salt thereof;

wherein fused rings A and B are each independently chosen from(C₅-C₁₀)cycloalkyl and (C₃-C₁₀)heterocyclyl;

m and n are each independently 1-8;

at each occurrence R⁴ is independently selected from —OH, —OR³,

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J;

at each occurrence R″ is independently a (C₂-C₁₀)alkanylene bonded to atleast one of a repeating unit and an end-blocking unit of the polymer attwo locations, wherein R″ is unsubstituted or substituted with at leastone J;

at each occurrence R² is independently chosen from —OH, —OR³, —NH₂,—NHR³, and —NR³ ₂;

at each occurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J;

fused rings A and B are each independently unsubstituted or substitutedwith at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and

wherein J independently at each occurrence is chosen from F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J and

a first substrate;

wherein the polymer is bonded to the first substrate.

Embodiment 77 provides the system of Embodiment 76, further comprising asecond substrate, wherein the polymer is bonded to the first and secondsubstrate such as to bond the first substrate to the second substratevia the polymer.

Embodiment 78 provides a method of using a tackifier compound having thestructure

or a salt thereof;

wherein fused rings A and B are each independently chosen from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl;

m and n are each independently 1-8;

at each occurrence R¹ is independently selected from —OH, —OR³, and

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J;

at each occurrence R² is independently chosen from —OH, —OR³, —NH₂,—NHR³, and —NR³ ₂;

at each occurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J;

fused rings A and B are each independently unsubstituted or substitutedwith at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and

wherein J independently at each occurrence is chosen from F, Cl, Br, OR,CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₃C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J;

the method comprising contacting the tackifier compound to a firstsubstrate such that the tackifier is bonded to the first substrate.

Embodiment 79 provides the method of Embodiment 78, further comprisingcontacting the tackifier compound to a second substrate such that thetackifier compound is bonded to the second substrate and such that thefirst substrate is bonded to the second substrate at least partially viathe tackifier compound.

Embodiment 80 provides the method of any one of Embodiments 78-79,wherein at least one R′ is C₁-C₁₀ alkenylene or C₁-C₁₀ alkynylene, themethod further comprising crosslinking the tackifier compound to providea polymer comprising a repeating unit comprising the structure

or a salt thereof;

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

wherein at each occurrence R″ is independently (C₂-C₁₀)alkanylene bondedto at least one of a repeating unit and an end-blocking unit of thepolymer at two locations, wherein R″ is unsubstituted or substitutedwith at leas one J.

Embodiment 81 provides the method of Embodiment 80, wherein thecrosslinking comprises at least one of application of heat, applicationof radiation, addition of a chemical crosslinker, and initiation of achemical crosslinker.

Embodiment 82 provides the method of Embodiment 81, wherein the chemicalcrosslinker comprises a free-radical initiator.

Embodiment 83 provides a method of making a tackifier compound,comprising:

contacting

-   -   a compound having the structure

and at least one acid anhydride having the structure

-   -   to provide a tackifier compound having the structure

or a salt thereof;

wherein fused rings A and B are each independently chosen from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl;

m and n are each independently 1-8;

at each occurrence R¹ is independently selected from —OH, —OR³, and

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is unsubstituted or substituted withat least one J;

at each occurrence R² is independently chosen from —OH, —OR³, —NH₂,—NHR³, and —NR³ ₂;

at each occurrence R³ is independently chosen from (C₁-C₁₀)alkanyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and (C₁-C₂₀)heteroaryl,wherein R³ is unsubstituted or substituted with at least one J;

fused rings A and B are each independently unsubstituted or substitutedwith at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and

wherein J independently at each occurrence is chosen from F, Cl, Br, OR,CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence chosen fromhydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

Embodiment 84 provides the method of Embodiment 3, wherein m=n=1.

Embodiment 85 provides the method of any one of Embodiments 83-84,wherein the anhydride is chosen from succinic anhydride, glutaricanhydride, and maleic anhydride.

Embodiment 86 provides the method of any one of Embodiments 83-85,wherein rings A and B form a ring system chosen from isosorbide,isomannide, and isoidide.

Embodiment 87 provides the method of any one of Embodiments 83-86wherein R′ is chosen from ethylene, propylene, and ethenylene.

Embodiment 88 provides the method of any one of Embodiments 83-87,wherein the method is a method of making a polymer, wherein at least oneR′ is (C₂-C₁₀)alkenylene or (C₃-C₁₀)alkynylene, the method furthercomprising crosslinking the tackifier compound to provide a polymercomprising a repeating unit having the structure

or a salt thereof;

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,

wherein at each occurrence R″ is independently a (C₂-C₁₀)alkanylenebonded to at least one of a repeating unit and an end-blocking unit ofthe polymer at two locations, wherein R″ is unsubstituted or substitutedwith at least one J.

Embodiment 89 provides the apparatus or method of any one or anycombination of Embodiments 1-88 optionally configured such that allelements or options recited are available to use or select from.

What is claimed is:
 1. A polymer comprising a repeating unit having thestructure:

or a salt thereof; wherein fused rings A and B are each independentlychosen from (C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl; m and n areeach independently 1-8; at each occurrence R⁴ is independently selectedfrom —OH, —OR³,

at each occurrence R′ is independently chosen from (C₂-C₁₀)alkanylene,(C₂-C₁₀)alkenylene, (C₂-C₁₀)alkynylene, C₅-C₂₀(arylene), and(C₁-C₂₀)heteroarylene, wherein R′ is substituted or unsubstituted; ateach occurrence R″ is independently a (C₂-C₁₀)alkanylene bonded to atleast one of a repeating unit and an end-blocking unit of the polymer attwo locations, wherein R″ is substituted or unsubstituted; at eachoccurrence R² is independently chosen from —OH, —OR³, —NH₂, —NHR³, and—NR³ ₂; at each occurrence R³ is independently chosen from(C₁-C₁₀)alkanyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, C₅-C₂₀(aryl), and(C₁-C₂₀)heteroaryl, wherein R³ is substituted or unsubstituted; andfused rings A and B are each independently substituted or unsubstituted.2. The polymer of claim 1, wherein the repeating unit has a structurechosen from:

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl, and wherein at each occurrence R⁴ isindependently selected from —OH, —OR³,


3. The polymer of claim 1, wherein the repeating unit has the structure:

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl and wherein at each occurrence R⁴ isindependently selected from —OH, —OR³,


4. The polymer of claim 1, wherein the repeating unit has the structure:

wherein at each occurrence L¹ and L² are independently chosen from abond and (C₁-C₁₀)alkyl.
 5. The polymer of claim 1, wherein the repeatingunit has a structure chosen from:

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,


6. The polymer of claim 1, wherein the repeating unit has the structure:

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,


7. The polymer of claim 1, wherein the repeating unit has the structure:


8. The polymer of claim 1, wherein rings A and B form a ring systemchosen from isosorbide, isomannide, and isoidide.
 9. The polymer ofclaim 1, wherein R″ is an alkanylene bonded to at least one of arepeating unit and an end-blocking unit of the polymer at two locationsand is chosen from ethylene, propylene, butylene, or pentylene.
 10. Thepolymer of claim 1, wherein the repeating unit has a structure chosenfrom:

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,


11. The polymer of claim 1, wherein the repeating unit has thestructure:

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,


12. The polymer of claim 1, wherein the repeating unit has thestructure:


13. The polymer of claim 1, wherein the repeating unit has a structurechosen from:

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,


14. The polymer of claim 1, wherein the repeating unit has a structurechosen from:

wherein at each occurrence R⁴ is independently selected from —OH, —OR³,


15. The polymer of claim 1, wherein the repeating unit has a structurechosen from:


16. A system comprising: the polymer of claim 1; and a first substrate;wherein the polymer is bonded to the first substrate.
 17. The system ofclaim 16, further comprising a second substrate, wherein the polymer isbonded to the first and second substrate to bond the first substrate tothe second substrate via the polymer.